Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs



United States Patent Int. Cl. pim 1/02 US. Cl. 862 1 Claim ABSTRACT OF THE DISCLOSURE Reactive dyestuffs fixed fast on natural and regenerated cellulose textile materials by printing same, drying, padding the print in an aqueous alkaline medium, and subsequently exposing the printed textile material to a passage of air at a temperature of 10 to 25 C.

The present invention provides a process for printing textile materials of natural or regenerated cellulose by means of reactive dyestuffs.

In the so-called two-phase printing process the reactive dyestuff is fixed fast on textile material of natural or regenerated cellulose by applying the dyestuff to the textile material in the first phase by means of a printing paste which contains water and a thickening agent and-after drying-padding the print in the second phase with an aqueous liquor which contains an agent having an alkaline reaction, steaming the material for to 30 seconds at about 110 to 115 C. and subsequently rinsing and soaping it, rinsing it again and finally drying it.

It has now been found that reactive dyestuffs can be fixed fast on textile materials of natural or regenerated cellulose, without using the steaming process, by printing the reactive dyestuff on the textile material in the first phase by means of a printing paste which contains water and a thickening agent and-after dryingpadding the print in the second phase with an aqueous liquor which contains an agent having an alkaline reaction and exposing it subsequently to an air passage.

As compared with the known two-phase steaming process the fixing process according to the present invention possesses several advantages. Since the steaming process is no longer necessary, a considerable amount of energy is saved per meter of printed material.

As compared with the two-phase steaming process the present invention possesses the advantage that the equilibrium reactive dyestuff+cellulose:reactive dyestuff-cellulose is shifted considerably in favour of the dyed cellulose. Thus, a reduction of the tinctorial strength can be 3,442,601 Patented May 6, 1969 avoided, particularly when dyestuffs are used which are easily resaponified at the binding dyestuff-fibre on steaming under the influence of alkalies. It is another disadvantage of the two-phase steaming process, which is avoided by the present invention, that the reducing influence of the cellulose occurring at the steaming temperature provokes changes of the tints not only when individual dyestuffs are used but also when dyestuff combinations for obtaining combination shades are applied. These changes cannot always be eliminated not even by adding oxidizing agents, such as, for example, the sodium salt of metanitrobeuzene sulfonic acid, to the printing paste. Finally, in a fixing process by steaming, the sharp outlines of the prints are affected so far as by the condensation of water on the printed fabric, the dyestuffs tend to flow and the printed spots cause the formation of so-called halos.

As reactive dyestuffs there can be used according to the process of the present invention different organic dyestuff classes, for example, azo dyestuffs and anthraquinone dyestuffs which contain at least one of the known reactive groups such as for example, B-hydroxyethylsulfone.sulfuric acid ester groups, vinylsulfone groups, dichlorotriazine groups, ethionylamino groups, N-alkyl-ethionylamino groups, 2,2,3,3-tetrafluorocyclobutane-l-carbonylamino groups, 2-fluoro-2-chloro-3,3-difluorocyclobutanel-carbonylamino groups, 2,2,3,B-tetrafluorocyclobutane-1- acryloylamino groups, vinylsulfonylamino groups or 2,3- dichloroquinoxaline radicals.

As agents having an alkaline reaction alkali metal hydroxides are preferably used. The concentration of the agent having an alkaline reaction influences the necessary time during which the print is exposed to the air passage to such an extent that with the increasing concentration of alkali the required time of residence of the printed material in the air is reduced. If, for example, cc. of sodium hydroxide solution (38 B.) are used per liter of padding liquor, the required minimum time of exposing the print to the air passage is about 10 seconds. As a rule, the minimum time of exposing the print to an air passage is between 1 and 5 minutes. In general, it is preferable to adjust the concentration of alkali in the padding liquor in such a way that the pH-value is be tween about 13 and 14. The optimum concentration of alkali and the time of residence of the printed material in the air must be regulated in each case according to the reactive dyestufi' used.

Suitable thickening agents are neutral thickening agents or thickeners having a weakly alkaline reaction such as, for example, alginates, different types of gum, or alkyl celluloses.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts and percentages being by weight unless otherwise stated:

EXAMPLE 1 40 parts of the dyestuff of the formula I SOaNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 30 seconds at C. The print thus obtained is then rinsed for about 10 minutes with cold water, treated for 3 minutes with Water which contains 3 parts of a complex forming agent on the base of a polymeric sodium meta-phosphate per 1000 parts by volume, subsequently soaped for about 10 minutes with an aqueous solution of 1% strength of a synthetic detergent (sodium salt of the condensation product of oleic acid and N-methyl taurine) and finally rinsed and dried.

A yellow print is obtained having a good fastness to light and wet processing.

EXAMPLE 2 40 parts of the dyestuff of the formula NaOaS SOGNQ SOzCH2OH20SO3Na are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of parts of the sodium salt of metal-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at C.

After having finished the fabric as described in Example 1, an orange print is obtained, having a good fastness to light and wet processing.

EXAMPLE 3 40 parts of the dyestuff described in Example 2 are mixed according to the method of the said example to form a printing paste. This printing paste is printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 18 C.

After having finished the fabric as described in Example 1, an orange print is obtained, having a good fastness to light and wet processing.

CH O SOaNa 4 EXAMPLE 4 60 parts of the dyestuff of the formula OH OCH;

| SO Na are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 450 parts of an aqueous methyl cellulose of 3%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at 15 C.

After having finished the fabric as described in Example 1, a red print is obtained, having a good fastness to light and wet processing.

EXAMPLE 5 50 parts of the dyestulf of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 450 parts of an aqueous methyl cellulose of 3%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a cotton fabric. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (3 8 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water and then exposed to an air passage for 3 minutes at 22 C.

After having finished the fabric as described in Example 1, a red print is obtained, having a good fastness to light and wet processing.

EXAMPLE 6 60 parts of the dyestuff of the formula NH: OH OH are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium metaphosphate per 1000 parts of thickener. After addition of parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 130 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (3 8 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000' parts by volume with water and then exposed to an air passage for 1 minute at 20 C.

After having finished the fabric as described in Example 1, a black print is obtained, having a good fastness to light and wet processing.

EXAMPLE 7 40 parts of the dyestutf of the formula NaOOC N=N N IF are dissolved in 300- parts of hot water after mixing with 50 parts of urea and introduced into 400' parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium metaphosphate per 1000 parts of thickener. After addition of parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 18 C.

After having finished the fabric as described in Example 1, a brown print is obtained, having a good fastness to light and wet processing.

SOsNB COONa SOg-CHz-CHrO-SOgNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 500 parts of an aqueous gum thickener of 2.5%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 80 parts of Water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100' parts by volume of sodium hydroxide solution (38 B.), 150

parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 23 C.

After having finished the fabric as described in Example 1, a blue print is obtained, having a good fastness to light and wet processing.

EXAMPLE 9 40 parts of the dyestulf of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alignate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium metaphosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 25 C.

After having finished the fabric as described in Example 1, a violet print is obtained, having a good fastness to light and wet processing.

EXAMPLE 10 40 parts of the dyestuff of the formula SOsNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 par-ts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 23 C.

After having finished the fabric as described in Example 1, a red print is obtained, having a good fastness to light and wet processing.

EXAMPLE 1.1

40 parts of the dyestuif of the formula OH l z CHaOQ-N=N 1 so CH=OH sO Na NaOaS r. z

are dissolved in 300 par-ts of hot 'water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of Water. The printing paste prepared in such a way is then printed on a linen fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 10 minutes at 23 C.

After having finished the fabric as described in Example 1, a red print is obtained, having a good fastness to light and wet processing.

EXAMPLE 12 40 parts of the dyestuff of the formula Naoas are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 22 C.

After having finished the fabric as described in Example 1, an orange print is obtained, having a good fast mess to light and wet processing.

EXAMPLE 13 40 parts of the dyestufi of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for minutes at 22 C.

After having finished the fabric as described in Example 1, an orange print is obtained, having a good fastness to light and wet processing.

8 EXAMPLE 14 40 parts of the dyestuff of the formula u HaC-O-NH 0H SOaNa I ily-o F2 N=N Nn-o o-on-b1n NBOsS SOaNB are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 20 C.

After having finished the fabric as described in Example 1, a violet print is obtained, having a good fastness to light and wet processing.

EXAMPLE 15 40 parts of the dyestuif of the formula SOaNa OH Q F NaOaS NH-CO H- H2 are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a linen fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 10 seconds at 15 C.

After having finished the fabric as described in Example 1, a golden yellow to orange print is obtained, having a good fastness to light and wet processing.

EMMPLE 16 40 parts of the dyestuff of the formula GFz-CF,

S OaNS by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded With a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for minutes at 20 C.

After having finished the fabric as described in Example 1, a yellow print is obtained, having a good fastness to light and wet processing.

EXAMPLE 17 40 parts of the dyestuff of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of Water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at 22 C.

After having finished the fabric as described in Example 1, a blue print is obtained, having a good fastness to light and wet processing.

EXAMPLE 18 40 parts of the dyestuff of the formula SOaNa are dissolved in 300 parts of hot Water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the Whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a Way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 20 C.

After having finished the fabric as described in Example 1, an orange print is obtained, having a good fastness to light and wet processing.

10 EXAMPLE 19 40 parts of the dyestuff of the formula G1 N N CH NH-k L01 l I N NaOiS SOaNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000' parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with Water, and then exposed to an air passage for 10 minutes at 20 C.

After having finished the fabric as described in Example 1, a red print is obtained, having a good fastness to light and wet processing.

We claim:

1. A process for producing fast prints on textile materials of natural or regenerated cellulose fibres, which comprises printing on said textile materials a printing paste containing a neutral to weakly alkaline thickening agent, water and an organic dyestuif containing at least one ,B-hydroxyethylsulfone sulfuric acid ester group, vinylsulfonyl group, dichlorotriazine group, ethionylamino group, N-alkyl-ethionylamino group, 2,2,3,3-tetrafluorocyclobutane 1 carbonylamino group, 2-fluoro-2- chloro 3,3 difiuorocyclobutane-1-carbonylamino group, 2,2,3,3-difluorocyclobutane-l-carbonylamino group, 2,2, 3,3-tetrafiuorocyclobutane-acroylamino group, vinylsulfonylamino group or 2,3-dichloroquinoxaline residue, after drying padding the print so obtained with an aqueous solution of an alkali metal hydroxide and subsequently exposing the print to an air passage at a temperature of about 10 to about 25 C.

References Cited UNITED STATES PATENTS 3,334,961 8/1967 Kuhne et al. 854.2

FOREIGN PATENTS 62/241 5/1962 Republic of South Africa.

NORMAN G. TORCHIN, Primary Examiner. T. J. HERBERT, JR., Assistant Examiner.

U.S. Cl. X.R. 854.2 

